RU2798123C1 - Cyclo-[(bis-1-imino-2-phenyl-1h-inden-3-ylydene)-1,4-phenylene-1,3,4-thiadiazole]sulfic acid with dye properties for paraffin, wool and nylon - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: invention is related to a new heterocyclic compound that can be used as a dye for dyeing paraffin, wool, nylon in various shades of red.

EFFECT: compound is proposed.

1 cl, 3 dwg, 4 ex

Description

The invention relates to the chemical industry, namely, to compounds that can be used as dyes for paraffin, wool, nylon.

A compound is known [Berezina G.R., Vorobyov Yu.G., Smirnov R.P. Synthesis and study of heterocyclic compounds based on 1,3-indanedione /JOH. 1998. V.68. Issue 6. S.1018-1020].

However, it does not have the property of a dye.

There are also known compounds that are structural analogues of the claimed compound [Berezina G.R., Vorobyov Yu.G. Synthesis and properties of macroheterocyclic compounds with fragments of substituted benzidine /JOH. 2006. V.76. Issue 8. S.1369-1374].

However, they do not have coloring properties and, therefore, cannot be used for dyeing in solutions, but can be used for the synthesis of macrocyclic compounds that do not have the property of an acid dye.

Aza dyes are known [Borodkin V.F. Chemistry of dyes. -M.: Chemistry, 1981. S. 95.97], which stain protein fibers, but do not stain capron, for example:

X R
HH orange red
H NHCOCH ₃ bright red
H NH ₂ bluish red

X
NH ₂ ruby
NO ₂ purple

Dyes based on 2-amino-5-mercapto-1,3,4-thiadiazoles [1. Shukurov S.Sh., Kukaniyev M.A. A new method for the synthesis of 2-amino-5-alkyl(aralkyl)thio-1,3,4-thiadiazoles // ZHORH. 1993. V.29. Issue 11. S.2327. 2. Hani R., Varadiya. Disperse dyes based on 2-amino-5-mercapto-1,3,4-thiadiazoles. //CHC. 2009. No. 10. S.1558-1563] dye only polyamide fibers in red-pink shades, for example:

X - NO ₂ , Cl, CH ₃ red-pink shades

The closest analogue are active copper-containing vinyl sulfone dyes [Patent 2068431 RF, IPC SW 62/51. Method for obtaining active vinylsulfone monoazo dyes / Prudchenko E.P., Sycheva O.V., Dynina I.A., Leznik R.F., Khrepinyuk T.E., Stepanenko V.O., Andrievsky A.M., Zhukova N. .A., Danilova T.S.; applicant and patent holder Moscow Research and Production Association "NIOPIK". - No. 5042702/05; dec. May 19, 1992; publ. 10/27/1996], which dye wool, silk, cellulose, natural and synthetic polyamide fibers blue:

The disadvantage of the prototype is the impossibility of painting in different shades of red.

The technical result consists in the search for a new compound that can be used as a dye that stains paraffin, wool and nylon in various shades of red.

This result is achieved by the compound cyclo-[(bis-1-imino-2-phenyl- 1H -inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid, which has the property of a dye for paraffin, wool and nylon formulas

The structure of this compound has been proven by elemental analysis, IR, and electron spectroscopy.

The invention is illustrated by drawings, where figure 1 shows the IR spectrum of cyclo-[(bis-1-imino-2-phenyl-1 H -inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole] sulfonic acid, figure 2 - electronic absorption spectrum of cyclo-[(bis-1-imino-2-phenyl-1 H -inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid in DMF, figure 3 - vykraska samples, where a is a sample obtained according to example 2, b - according to example 3, in - according to example 4.

In the IR spectra of the claimed compound (figure 1) you can select a number of common absorption bands with analogue [Berezina G.R. Thermodynamics of dissolution of asymmetric macroheterocyclic compounds with thiadiazole fragments in polar solvents /Journal of Physical Chemistry, 2021. V.95, No. 6, p. 890-893].

In the electronic spectra of cyclo-[(bis-1-imino-2-phenyl- 1H -inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid absorption is observed at 280, 330, 460 nm (logε 4.5), recorded in DMF (figure 2). The nature of the spectrum shows that the compound exists in solution predominantly in the form of a monomer.

Cyclo-[(bis-1-imino-2-phenyl-1 H -inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid is a dark red substance with solubility in DMF, water, ethanol, chloroform.

The claimed new compound has the property of a dye and can be used for dyeing paraffin, wool and nylon.

To obtain the target product, the following substances are used:

Phthalic anhydride GOST 7119-77,

Phenylacetic acid GOST 931666,

sodium metal TU 6-09-356-77,

sodium acetate GOST 199-78,

glacial acetic acid GOST 19814-74,

ammonium acetic GOST 3117-78,

methanol GOST 2222-95,

ethanol GOST R 55878-2013,

hydrochloric acid GOST 857-95,

hydrogen peroxide GOST 177-88,

hydrazine sulfate GOST 5841-74;

ammonium thiocyanate GOST 27067-86;

chloroform GOST 20015-88,

acetic anhydride GOST 5815-77,

sulfuric acid (conc. 94%) GOST 2184-2013,

1,4-phenylenediamine GOST 5234-78,

DMF GOST 20289-74.

The claimed compound is obtained as follows: first, 2-phenylindanedione diimine is synthesized by the interaction of phthalic anhydride, phenylacetic acid, sodium acetate, sodium metal, methyl alcohol, ammonium acetate and glacial acetic acid, then the resulting compound is reacted with 2,5-diamino-1,3 ,4-thiadiazole in a ratio of 1:1 and then carry out the sulfonation of the dimer. The sulfonated dimer is then reacted with 2-phenylindanedione diimine and 1,4-phenylenediamine in a ratio of 1:1:1.

Example 1Synthesis target product.

Synthesis of diimine 2-phenylindanedione

In a three-necked flask equipped with a reflux condenser, 100 g of phthalic anhydride, 110 g of phenylacetic acid and 2.6 g of freshly fused sodium acetate are added with a thermometer. The mixture is heated to 240°C and the water is distilled off for 2 hours. Next, the product is cooled to 95 °C and dissolved in 40 ml of boiling ethanol. The solution is filtered, cooled, the precipitated crystals of benzalphthalide are filtered off and washed with 50 ml of cold alcohol, so pl. 96-98 °С. Next, 22 g of benzalphthalide is dissolved by heating in 150 ml of methyl alcohol and 50 ml of a 6% solution of sodium methoxide is added to the solution, the solution becomes dark red. After distillation of ethanol, needle-shaped red crystals are isolated, which are dissolved in water and acidified with hydrochloric acid. Yield: 2-phenylindanedione 22 g (90%), creamy-white substance with t _pl =145 °C. Then 15 g of the product are dissolved in 50 ml of glacial acetic acid and 70 g of ammonium acetate are gradually added. The mixture is boiled for 3 hours, cooled and left for a day, then filtered, the precipitate is washed with water and dried.

Yield of diimine 2-phenylindanedione (75%). Substance of orange color in powder with t _pl =180 °C.

Found, %: С 78.88; H 5.55; N 12.56. C ₁₅ H ₁₂ N ₂ .

Calculated, %: С 81.82; H 5.45; N 12.73.

Synthesis of 2,5-diamino-1,3,4-thiadiazole

A). Synthesis of dithiourea. 66.3 g (0.5 mol) of hydrazine sulfate and 77.7 g (1 mol) of ammonium thiocyanate are dissolved in 100 ml of distilled water, the solution is heated on a boiling water bath; 40 minutes after heating, the solution becomes light yellow and a reaction is observed with the release of ammonia and hydrogen sulfide. After 20-40 min. a white crystalline precipitate falls out of the solution. The contents of the flask are heated with stirring for 5 hours, then the solution is precipitated by adding 50 ml of water. The precipitate is filtered off and washed with ice water. The washed precipitate is dissolved in boiling water and filtered off. The filtrate is precipitated, the precipitate is decanted and dried at 70°C.

Yield: 49.34 g (64.5%), m.p. 206-208 °С.

Found, %: С 15.5; H 3.8; N 37.23; S 42.21. C ₂ H ₆ N ₄ S ₂ .

Calculated, %: С 16; H 4; N 37.33; S 42.67.

B). 15 g (0.1 mol) of dithiourea and 350 ml of distilled water are added to the flask, heated with stirring to 90 °C and 15 ml of 30% hydrogen peroxide are added and shaken vigorously. The sulfur coagulates into a lump, the orange solution is filtered off. Hydrogen sulfide is passed through the filtrate for 30-40 minutes until an off-white solution is formed, then the filtrate is evaporated by 2.3 volumes, cooled to 0-5 °C. The precipitated white crystals are filtered off and dried.

Yield 5.1 g (58%), mp. 204-205 °С.

Found, %: С 21.41; H 3.38; N 43.47; S 26.41. _{C2H4N4S . _}

Calculated, %: From 20.69; H 3.45; No. 48.28; S 27.58.

Synthesis of cyclo-[(bis-1-imino-2-phenyl-1H-inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid

A). Synthesis of N ³ -[3-amino-2-phenyl-1H-inden-1-ylidene]-1,3,4-thiadiazole-2,5-diamine. 0.15 g (0.7 mmol) of 2-phenylindanedione diimine and 0.08 g (0.7 mmol) of 2,5-diamino-1,3,4-thiadiazole are added to a flask equipped with a reflux condenser and a stirrer and boil in 7 ml of ethanol for 30 hours. The precipitate formed during cooling of the reaction mixture was filtered off and dried at 80°C. The product is a red powder, m.p. 191 °C, soluble in ethyl alcohol, DMF; poorly soluble in acetone.

Exit N³-[3-amino-2-phenyl-1H-inden-1-ylidene]-1,3,4-thiadiazole-2,5-diamine: 0.17 g (76.7%).

IR spectrum, ν, cm ^-1 : (NH ₂ ) 3450; (C=N) 1635; (C=C) 1547, 1435; (C-C) 1255; (CN) 1114; (CH) 758; (CS) 699.

ESP, λ _max , nm: in ethanol: 459; in acetone: 417.

Found, %: С 63.47; H 4.51; N 20.91; S 8.67. C ₁₇ H ₁₃ N ₅ S.

Calculated, %: С 63.93; H 4.10; N 21.9,; S 10.04.

B). Synthesis of 1-[(5-amino-1,3,4-thiadiazol-3-yl)imino]-2,3-dihydro-3-imino-2-phenyl-1H-inden-2-sulfonic acid. To a mixture of 0.05 g (0.15 mmol) N ³ -[3-amino-2-phenyl-1H-inden-1-ylidene]-1,3,4-thiadiazole-2,5-diamine with 3 ml of chloroform while stirring, 1 ml of acetic anhydride and 2 ml of 94% sulfuric acid are slowly added dropwise. Next, the reaction mass is kept under stirring for 30 minutes. The resulting mixture was cooled in an ice bath for 3.5 hours. The product is isolated by salting out. The precipitate that formed was filtered off and dried at 80°C.

Yield of 1-[(5-amino-1,3,4-thiadiazol-3-yl)imino]-2,3-dihydro-3-imino-2-phenyl-1 H -inden-2-sulfonic acid 0.02 g (34.77%).

The product is a burgundy powder, soluble in water, ethyl alcohol.

IR spectrum, ν, cm ^-1 : (NH ₂ ) 3471; (NH) 3415; (C=N) 1626; (C=C) 1506.

1432; (C-C) 864; (C-N) 991; (C-H) 759; (C-S) 620; (C-S) 620; (OH) 1257; (S=O) 1142.

ESP, λ _max , nm: in water: 469.

Found, %: С 49.37; H 3.10; N 16.65; S 15.04; About 12.56. C ₁₇ H ₁₃ N ₅ S ₂ O ₃ .

Calculated, %: С 51.11; H 3.28; N 17.54; S 16.05; About 12.02.

IN). 0.1 g (0.26 mmol) of N²,N⁵-bis-[1-imino-2-phenyl-1H-inden-3-yl]-1,3,4-thiadiazol-2,5-diamine and 0.06 g (0.26 mmol) diimine 2-phenylindanedione (in a molar ratio of 1:1) is heated in 7 ml of DMF at boiling for 28 hours, then 0.02 g (0.26 mmol) of 1,4-phenylenediamine is added and heating is continued for another 20 hours. The reaction mass is cooled in ice bath for 2.5 hours, isolated by salting out. The precipitate formed is filtered off and dried. The product is a dark red powder, soluble in DMF, water, ethanol.

Yield of cyclo-[(bis-1-imino-2-phenyl-1Н-inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid 0.09 g (52%).

IR spectrum, ν, cm ^-1 : (С-S) 759, (С-N) 1368, (С-С) 1432, (С=N) 1555, (С=С) 1610, 1630, (С-Н ) 2825, 3167, (NH) 3454.

ESP, λ _max , nm (log ε) : in DMF: 280, 330, 460 (4.5); in ethanol, 230, 285, 465 (3.9), in water: 475.

Found, %: С 66.53; H 3.43; N 11.95; S 8.85; About 6.85. C ₃₈ H ₂₄ N ₆ S ₂ O ₃ .

Calculated, %: C 67.46; H 3.54; N 12.43; S 9.47; About 7.10.

Example 2 Use of cyclo-[(bis-1-imino-2-phenyl-1H-inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid as a wax stain.

A sample of paraffin weighing 1.25 g is placed in a porcelain cup and heated until melted, a solution of 0.007 g of cyclo-[(bis-1-imino-2-phenyl-1 H -inden-3-ylidene)-1,4-phenylene- 1,3,4-thiadiazole]sulfonic acid in 3 ml of DMF, heated until DMF is completely removed, and the resulting mass is poured onto a glass slide. The sample has uniform coloring and bright color.

A sample of stained paraffin (Fig. 3a) is attached.

Example 3 . Use of cyclo-[(bis-1-imino-2-phenyl-1H-inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid as an acid dye for wool. Dyeing was carried out according to the method [Laboratory workshop on the use of dyes /Ed. Melnikova B.N. M.: Chemistry - 1972. S.7-9].

A sample of wool fiber weighing 1 g is placed in a dye bath of the composition (g/l):

Cyclo-[(bis-1-imino-2-phenyl-1H-inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid 6

Glauber's salt 40 bath module 50

Within 15-30 min. the bath is heated to 60 °C and maintained at this temperature for 40 minutes and 20 minutes in a bath cooling to 30 °C.

The sample is squeezed, washed thoroughly with warm, then cold water, and treated with a sulfuric acid solution of the composition (ml):

sulfuric acid 1 water 50

The sample is squeezed out, thoroughly washed with warm, then cold water, and dried. A color sample (Fig. 3b) is attached.

Example 4 . Use of cyclo-[(bis-1-imino-2-phenyl-1H-inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid as an acid dye for capron. Dyeing was carried out according to the method [Laboratory workshop on the use of dyes /Edited by Melnikov B.N. M.: Chemistry-1972. S.7-14].

A sample of nylon fiber weighing 1 g is placed in a dye bath with the composition (g/l):

Cyclo-[(bis-1-imino-2-phenyl-1H-inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acids 6

Glauber's salt 40 bath module 50

Within 15-30 min. the bath is heated to 60 °C and maintained at this temperature for 40 minutes and 20 minutes in a bath cooling to 30 °C.

The sample is squeezed, washed thoroughly with warm, then cold water, and treated with a sulfuric acid solution of the composition (ml):

sulfuric acid 1 water 50

The sample is squeezed out, thoroughly washed with warm, then cold water, and dried. A color sample (Fig. 3c) is attached.

The samples were obtained with various shades of red.

Claims (3)

Cyclo-[(bis-1-imino-2-phenyl-1H-inden-3-ylidene)-1,4-phenylene-1,3,4-thiadiazole]sulfonic acid of the formula

, having the property of a dye for paraffin, wool and nylon.

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